Oxyalkylated phenol-aldehyde resins



3,038 881 OXYALKYLATED PHENbL-ALDEHYDE RESINS Melvin De Groote, St. Louis, Mo., assignor to Petroiite Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Filed Jan. 8, 1959, Ser. No. 785,558 Claims. (Cl. 260--58) This application is a continuation-in-part of application Serial No. 383,928, filed October 2, 1953 (now U.S. Patent 2,792,366 dated May 14, 1957), Serial Nos. 398,631; 398,632; and 398,633, all filed December 16, 1958, and all now abandoned, and Serial Nos. 639,200; 639,201; 639,202; and 639,203, all filed February 11, 1957. The latter four applications are respectively divisions of Serial Nos. 418,784; 418,785; 418,786; and 418,787, all filed March 25, 1954, and now issued respectively as US. Patents 2,819,224; 2,819,225; 2,819,226; and 2,819,227, all dated January 7, 1958.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the Water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

Attention is directed to applications Serial Nos. 383,928; 398,631; 398,632; and 698,633. These applications are directed to processes for breaking petroleum emulsions employing a demulsifier including products obtained by condensing certain phenol aldehyde resins, therein described in detail, with certain basic secondary amines, also therein described in detail, and respectively glyoxal, pyruvic aldehyde, alpha-hydroxyadipaldehyde, and alphagamma-dimethyl-alpha-methoxymethylglutaraldehyde.

The present invention may be characterized in that it is concerned with a process for oxyalkylating by means of monoepoxides the reaction products obtained by the procedure described previously by reference to co-pending applications Serial Nos. 383,928; 398,631; 398,632 and 398,633.

The products obtained by oxyalkyl-ation with a monoepoxide such as ethylene oxide, propylene oxide, butylene oxide or the like, can be subjected to further reaction with a product having both a nitrogen group and 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U.S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

The new products are useful as Wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as Wetting agents and detergents in the acid Washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade Wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics spray oils, Water-repellent textile finishes; as lubricants, etc.

In the present instance the various condensation prod ucts as such or in the form of the free base or in the form of the acetate, may not necessarily be xylenesolublo although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethyleneglycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropri- 3,838,881 Patented June 12, 1962 ate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there Will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is made again to US. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this test with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the water-inoil type is characterized by the fact that a 50-50 solution in xylene, or its equivalent, when mixed with one to three volumes of water and shaken will produce an emulsion.

For purpose of convenience, What is said hereinafter will be divided into six parts:

Part 1 is' concerned with phenol-aldehyde resins suitable for condensation;

Part 2 is concerned With suitable secondary amines which can be employed in conjunction with the resins in the condensation procedure;

Ifart 3 is concerned with the condensation procedure as such;

Part 4 is concerned with reactions involving the intermediates obtained in the manner described in Part 3, preceding, and certain alpha-beta monoepoxides having not over 4 carbon atoms;

Part 5 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds of reaction prodnets; and

Part 6 is concerned with the uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U.S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecyllphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U.S. Patent No. 2,499,370, reference is made also to the following U. S. patents: Nos. 2,499,365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atoms also being very satisfactory. The increased cost of the C and C carbon atoms phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

2 As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, US. Patent No. 2,499,365, dated March 7, 1950, to DeGroote and Keiser, such as Example 71a.

Reference has been made to an earlier formula which was in essence an over-simplification representing a phenolformaldehyde resin. Actually, some other aldehyde, such as acetaldehyde, propionaldehyde, or butyraldehyde, may be used. The resin unit can be exemplified thus:

R n R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin.

. As previously stated, the preparation of resins of the kind herein employed as reactants is well known. See US. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense, or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proeeeded more rapidly in the presence of a small amount of free base. The amount may be as small as a 200th of a percent and as much as a few tenths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i.e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I have found no reason for using other than those which are lowest in price and most readily available commercially. For purpose of convenience suitable resins are characterized in the following table:

TABLE I Moi. wt. Ex- Position R of resin ample R of R derived n molecule number 0111 (based on n+2) Tertiary butyl Para. Formal- 3. 5 882. 5

dehyde Secondary butyl. Ortho do 3. 5 882. 5 Tertiary amyl Para do 3.5 959. 5

Mixed secondary Ortho do 3. 5 805. 5

and tertiary amyl.

Prop Para 3. 5 805. 5 Tertiary hexyi. 3. 5 1, 036. 5

Oct 3. 5 l, 190. 5 Nonyl 3. 5 1,267. 5 DecyL. 3. 5 1, 344. 5 Dodecyl 3.5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyi... 3. 5 1,022. 5

Nonyl 3. 5 1, 330. 5 Tertiary butyl d 3. 5 1, 071. 5

Tertiary amyl do.. 3. 5 1, 148. 5

Nonyl (ln 3. 5 1. 456. 5

TABLE IContinued Mol.wt.

Ex. R::: of resin ample R Position derived n molecule number of R irom (based on n+2) 17a Tertiary butyl Para Propional- 3.5 1,008.5

dehyde. 18a Tertiary amyi -1 d0 o 3.5 1,085.5 19a Nonyl do o 3.5 1,393.5 20a Tertiary butyl do Formal- 4.2 996.6

dehyde Tertiary amyl. 4. 2 1, 083. 4 Nonyl 4.2 1,430.6 Tertiarybut 4.8 1,094.4 Tertiary amyl. 4. 8 1,189.6 4.8 1570.4 1.5 604.0 1.5 653.0. 1.5 688.0-

PART 2 a variety of secondary amines free from a primary amino group may be employed. These amines fall into five categories, as indicated previously.

One category consists of strongly basic secondary monoamines free from hydroxyl groups whose composition may be indicated thus:

R! in which R represents a mo-novalent alkyl, ali'cyclic, arylalkyl radical and may be heterocyclic in a few instancesas in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a; similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, ofcourse, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylarnine, dibutyl- As noted previously,

amine, diamylarnine, dihexylamine, dioctylamine, and di'- nonylarnine. Other amines include bis(1,3-dimethyl' butyl)amine. There are, of course, a variety of primary amines which can be reacted With an alkylating agent such as dimethylsulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines. within the herein specified limitations. For example, one can methylate alphamethylbenzylamine, or benzylamine: itself, to produce a suitable reactant. Needless to say, one can use secondary amines such as dicyclohexylamine, dibutylarnine or amines containing one cylohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexylamine, ethylbenzylamine, etc,

Other suitable compounds are exemplified by Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in US. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenXy-alpha-Inethylethylamine, and betaphenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by The secondary category represents secondary amines which are hydroxylated monoamines. These may be illustrated by diethanolamine, methylethanolamine, dipropanolamine, dibutanolamine and ethylpropanolamine. Suitable primary amines which can be so converted into secondary amines include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc.

Other suitable amines include Z-amino-l-butanol, 2- amino-Z-methyl-l-propanol, 2 amino 2 methyl 1,3- propanediol, 2-amino-2-ethyl-1,3-propanediol, and ms- (hydroxylmethyl) aminoethane. Another example of such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Other suitable compounds are the following:

NH HOO IL (C2H5OC2H4OC2H4OC2H4) /NH HOC H; (C3HQOCHECH(CH3)O(GH3)GHCH2) H0 02m (CHQOCHQCHZOCHZCHQOCHzCHz) HOC2H4 (CH OOH OHQCHQCH CH CH HOCgH; or comparable compounds having two hydroxylated groups of different lengths as in (HOCHQCH OCH CHgOCH CHg) HO C1114 Other examples of suitable amines include alphamethylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalklating agent as previously described; betaethylhexylbutanolamine, diglycerylamine, etc. Another type of amine which is of particular interest because it includes a very definite hydrophile group include sugar amines such as glucamine, galactarnine and fructamine, such as N- hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by ITIH H0.CH2.G.CH2OH CH CHs.( J.CH2OH NH CHa.? .CH2OH See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in US. Patent No. 2,510,063, dated June 6, 1950, to Bn'ed. Still other examples are illustrated by treatment of certain secondary amines, such as the following, With a mole of an oxyalkylating agent as described; phenoxyetliylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamiue.

Polyamines free from a hydroxyl group may be illustrated by the following:

CH CH The fourth category consists of polyamines having hydroxylated groups which may be characterized by the following:

HO 0 H; 0 11 013 CH CH Suitable cyclic amidines which may or may not have a hydroxyl group but are free from primary amino groups may be illustrated by the following:

A compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a 2 compound such as N-C H2 C 17 asC 1? CH: C 2H,.NH: Z-heptadecyl, l-aminoethylimidazoline which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of Z-heptadecyl,l-aminoethylimidazoline, wh1ch can be illustrated by the following formula:

I N-CH2 CHEM-C Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, 2- heptadecyl,l-aminoethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amine group. If ethylene imine is employed, the net result is simply to convert Z-heptadecyl,l-arninoethylimidazoline into 2-heptadecyl,l-diethylenediaminoimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, 1.e., one having both ethylene group and a propylene group between nitrogen atoms.

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

The herein described amine-modified resins are obtained from a difunctional aldehyde and not formaldehyde. Generally speaking, the objective in the prepara tion of these amine-modified resins is to obtain a heatconvertible compound even by not using formaldehyde.

It is not necessary to point out the complications involved when glyoxal pyruvic aldehyde, alpha-hydroxyadipaldehyde, and alpha-gamma-dimethyl-alpha-methoxymethylglutaraldehyde is used. See, for example, US. Patent No. 2,031,557 to Bruson. Since the condensation products obtained are not heat-convertible and since temperatures up to C. or thereabouts maybe employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned US. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, I have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as noted, and it is not necessary to have a single phase system for reaction.

Glyoxal is available as a 30% aqueous solution. In this way it is comparable to formaldehyde which is available as a 37% aqueous solution, and is sometimes used in more dilute form. Pyruvic aldehyde is available as a 36% aqueous solution. Alpha-hydroxyadipaldehyde is available as a 50-55% aqueous solution. Alpha-gammadimethyl-alpha-methoxymethylglutaraldehyde is available as the anhydrous material. In fact it polymerizes on standing in the presence of water. I have found no difficulty in promoting the condensation reaction although at times it is desirable to add some solvent having a com mon solvent effect. Thus an oxygenated solvent may or may not be employed. Such solvent may be employed in combination with a hydrocarbon solvent such as xylene. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick, viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the condensation products obtained are invariably dark and particularly reddish or dark red in color.

By and large, the melting point of the condensate is apt to be higher than of comparable condensates obtained by the use of formaldehyde, or furfural. As has been suggested previously, this apparently is due to the difunctiona1 property of glyoxal, pyruvic aldehyde, alpha-hydroxyadipaldehyde, and alpha-gamma-dimethyl-alpha-methoxymethylgutaraldehyde. Indeed, depending on the resin selected and the amine selected the condensate product or reaction mass on a solvent-free basis is apt to be harder than the original resin itself. This is particularly true when all the amino hydrogen atoms present in the amine have entered into reaction.

The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished prodnot into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene or the like, depends primarily on cost, i.e., the use of the most economical solvent and also on three other factors, two of which have been mentioned previous- 1y; (:1) is the solvent to remain in the reaction mass without removal; (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation; and the third factor is this (c) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a waterwash to remove any unreacted low molal soluble amine, if employed and present after reaction. Such procedures are Well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no advantage in using a low temperature, approximately room temperature, at the start of the reaction although this is sometimes done purely as a matter of convenience. Indeed, using glyoxal pyruvic aldehyde, alpha-hydroxyadipaldehyde, and alpha-gamma-dimethyl-alpha-methoxymethylglutaraldehyde I have usually done nothing more than prepare the reaction mixture, add a suitable amount of xylene, and reflux for approximately 3 to 6 /2 hours at temperatures varying, as the case may be, from 135 to 160 C. Where the amine has a comparatively low basicity I have sometimes added a small amount or approximately 1% of sodium methylate.

However, using a xylene-benzene mixture, for instance, approximately 170- parts of benzene and 35 parts of xylene, and a phase-separating trap to eliminate water, I have found that I could employ temperatures between and 'C., and eliminate the water of condensation by refluxing at this temperature. However, I have found no particular advantage in using this low temperature over and above the high temperature previously noted.

Example 1b The resin employed was the one previously designated as 26a and had a molecular weight of approximately 600. 175 grams of this resin were dissolved in an equal weight of xylene and 61 grams of di-isopropanolamine added. 58 grams of glyoxal (30% aqueous solution) were added and the mixture stirred for about 30 minutes and then the temperature allowed to rise to C., where it was allowed to reflux for 6 hours. During this refluxing period a phase-separating trap was used to remove the water of formation. At the end of this time the reaction was complete and the product was obtained in the form of a xylene solution. A small sample was evaporated to eliminate the Xylene. The resultant product was a highly viscous, tacky material, being black in color with a reddish tinge.

Similar products were prepared as indicated in the following table:

TABLE II Glyoxal Solvent Max. Resin Amt, (30% aq. (xylene un- Tirnc temp Ex. No. amt, Secondary amme grams s01), less otherperiod, during grams grams Wise noted), hrs. reaction,

grams C.

175 Di-isopropanolamine 61 58 170 7 D i-n-butylamine 65 48 160 6 160 150 D1-ethylamine 37 48 5 143 150 Di-cyclohexylamine r 91 48 155 7 170 300 Mprpholine 87 96 305 6 145 300 D 1 2-ethyll 1exylamine 1 241 96 290 4. 5 163 225 B1 s;(1, 3-d1methylbutyl)amine 139 72 235 225 Dr-isopropanolamine 100 72 230 3 225 a-Methylbenzyl-ethanolamine. 124 72 235 3 157 225 Diethanolamine 79 72 220 2. 5 158 225 Aminoethyl ethanolamine 78 72 230 2 140 225 Diethanolamine 79 72 "55170 3 100 79 72 55-170 3 98 h 131. 5 12s 55-170 a 99 225 Dnsopropanol inc 174 128 235 1. 75 130 236 D1-isopropylamine 61 58 231 7' 145 197 Di-n-butylamine. 65 48 192 6 160 197 Diethylamine. 37 48 203 5 145 197 Di-eyclohexylamine 91 48 185 7 393 Morpholine 87 96 384 6. 5 155 393 D1(2-ethylhexyl)amine 241 96 398 5.. 0 197 N :methylaniline 54 48 102 4 170 295 Di-(beta-phenylethyl) amine 169 72 300 4. 5 160 295 Di-isopropanolamine 100 72 200 3 155 225 Di-ethanolamine 79 72 305 2. 75 158 188 Di-isopropylamine. 61 58 220 8 145 188 do 11 65 48 178 5 162 188 Di-etl1ylaml11e 37 48 6 145 374 Di-cyclohexylamine 1 91 48 196 7 163 374 Morphollne 87 96 370 6.. 5 155 188 D1-(2ethylhexyl) amine 241 96 378 4.. 5 168 280 N:methylanillne 54 48 198 5 170 280 Dl-(beta-phenylethyDamine. 169 72 290 4. 5 158 280 Di-isopropanolamlne 100 72 270 3 155 280 Di-ethanolamine 79 72 270 2. 75 158 Nora-1n the above examples no catalyst was added. In some duplications of the above small amounts of 12 Similar products were prepared as indicated in the following table:

TABLE III Methyl Solvent Max. Resin Amt, Glyoxal (xylene un- Time temp. Ex. No. amt, Secondary amine grams (36% sq. less otherperiod, during grams sol. Wise noted), hrs. reaction,

grams grams C.

175 Di-isopropanol-amlne 61 61. 5 180 6. 75 144 150 Di-n-butylamine 65 50. 165 6. 158 150 DLethylamine 37 50.0 156 5. 5 145 150 Di-cyclohexyl-amine 91 50. 0 150 6. 75 168 300 Morpholine 87 100. O 310 5. 75 143 300 Di-Z-ethylhexyl-amine 241 100. 0 288 5. 00 165 225 Bis-(1, S-dnnethyl-butyhamme. 139 75.0 237 225 Di-isopropanol-amine 100 75. 0 233 3. 5 165 225 a-Methylbenzyl-ethanolamine.. 124 75. 0 238 3. 5 160 225 Di-ethauolamine 79 75. 0 230 3. 0 161 225 Aminoethyl ethanolamine. 78 75.0 235 2. 5 145 Diethanolamine 79 75. 0 **55170 3. 5 105 79 75.0 55-170 3. 5 100 131. 5 133.0 "55-170 3. 5 101 174 133.0 240 2.0 125 Di-isopropylamine 61 61. 5 238 7. 5 160 Di-n-butylamlne 65 50. 0 155 6. 5 165 197 37 50.0 205 5. 5 150 197 91 50.0 180 6. 75 155 a 393 87 100 380 7. 0 160 393 241 100 399 5. 75 .65

197 54 50.0 101 4. 5 168 295 169 75.0 303 5. O 160 295 100 75. 0 205 3. 75 160 225 79 75. 0 300 3. 0 140 188 61 61. 5 222 7. 75 166 188 65 50.0 180 6.0 150 188 Di-ethylamine. 37 50. 0 178 6. 5 162 29c. 374 Di-eyclohexylamine 91 50.0 194 7. 5 160 30c. 374 Morpholine 87 100 374 7.0 170 188 Di-(2etl1ylhexyl)am1ne 241 100 379 5. 0 165 280 N-methylaniline 4 50 200 6. 0 168 280 Di-(beta-phenylethyl)amine. 169 75 295 6. 5 155 30 m-iso ropauolam e 100 75 273 4. 0 153 230 Diethanolami e 79 75 273 3. 0 155 catalyst were added up to 1% to 2% of either powdered caustic soda or powdered sodium methylate. No advantage was noted in the use of a catalyst provided the amine was sufiiciently basic.

In Examples 12b, 13b and 1412 indicated by the double asterisk the solvent was a mixture of 170 parts of benzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 145 and 1512 where the ratio was 1 to 3.5 to 1.75 in both instances.

In Examples 1b through 155 the resin employed was the one identified as Example 26a. in Examples 165 through 255 the resin employed was the one identified as Example 29a, and in Examples 265 through 351) the resin employed was identified as Example 365.

Example The resin employed was the one previously designated as 26a and had a molecular weight of approximately 600. 175 grams of this resin were dissolved in slightly more than an equal Weight of xylene and 61 grams of di-isopropanolamine added. 61.5 grams of methyl glyoxal (36% aqueous solution) were added and the mixture stirred for about minutes and then the temperature allowed to rise to 144 C., where it was allowed to reflux for 6.75 hours. During this refluxing period a phaseseparating trap was used to remove the water of formation. At the end of this time the reaction was complete and the product was obtained in the form of a xylene solution. A small sample was exaporated to eliminate the xylene. The resultant product was a highly viscous, tacky material, being black in color with a reddish tinge.

Nore.-In the above examples no catalyst was added. In some duplications of the above small amounts of catalyst were added up to 1% to 2% of either powdered caustic soda or powdered sodium methylate. No advantage was noted in the use of a catalyst provided the amine was sufficiently basic.

In Examples 120, 13c and indicated by the double asterisk the solvent was a mixture of 170 parts'of benzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 140 and where the ratio was 1 to 3.5 to 1.75 in both instances.

In examples 1c through 150 the resin employed was the one identified as Example 26a. In Examples through 25c the resin employed was the one identified as Example 29a, and in Examples 260 through 350 the resin employed was identified as Example 360.

Example In! The resin employed was the one previously designated as 26a and had a molecular weight of approximately 600. grams of this resin were dissolved in slightly more than an equal weight of xylene and 61 grams of di-iso propanolamine added. 80 grams of alpha-hydroxyadipaldehyde (50% aqueous solution) were added and the mixture stirred for about 40 minutes and then the temperature allowed to rise to 142 C., where it was allowed to reflux for 7 hours at a miximum temperature of 145 C. During this refluxing period a phase-separating trap was used to remove the water of formation, and also the water of solution. At the end of this time the reaction was complete and the product was obtained in the form of a xylene solution. A small sample was evaporated to eliminate the xylene. The resultant product was an almost hard somewhat tacky material, being blackish red in color.

Similar products were prepared as indicated in the Example 19 following table: The resin employed was the one previously designated TABLE IV Alpha- Solvent Max. Resin Amt., hydroxy (xylene un- Time temp. EX. No. amt., Secondary amine grams Adipal less otherperiod, during gram s dehyde wise noted), hrs. reaction,

50% aq. grams C. sol.,grams 175 Di-isopropal". olarnine 61 80.0 190 7.0 145 150 Di-n-butylaznine 65 65. 164 6. O 158 150 Diethylarnine 37 65. 0 154 5. 0 144 150 Di-cyclohexylamine. 91 65. 0 150 6. 0 167 300 Morpholine 87 130.0 306 5. 75 143 300 Di-2-ethylhexylaruine 241 130.0 287 5.5 164 225 Bis-(1,3-dimethylbutyl) amine... 139 97. 238

225 Di-isopropanol amine 100 97. 5 232 3. 5 166 225 a-Methylbenzyl ethanolamine 124 97. 5 237 3. 5 160 225 Di-ethanolamine 79 97. 5 222 3. 5 161 225 Aminoethyl ethanolamine 78 97.5 234 2. 5 146 225 Diethanolamine 79 97.5 55-170 4.0 107 225 Diisopropanolamine 174 173.0 238 2.0 125 236 Di-isopropyl amine. 61 80. 0 236 7. 5 150 197 Di-n-butylamine 65 65. 0 194 6. 5 166 197 Di-ethylamine. 37 65. O 203 5. 5 148 197 Di-cyclohexylam 91 65. 0 178 6. 5 156 393 lworpholinefl. 87 130.0 377 6. 75 160 393 Di-(2-ethyll1exyl 241 130. 0 398 6. 0 166 197 N-methylaniline 54 65. 0 100 5. 0 167 295 Di-(beta-phenylethyDam 169 97. 5 302 5. 5 160 295 Di-isopropanolamine 100 97. 5 204 4. 0 160 d 225 Di-ethanolamine 79 97. 5 298 3. 0 143 2611.- 188 Di-isopropylamine 61 80. O 220 7. 5 168 27d 188 Di-n-butylamine 65 65. 0 181 6. 0 150 28d 188 Di-ethylamine 37 65. 0 177 6. 5 162 291L 374 Di-cyclohexylamine--. 91 65. 0 193 7. 0 163 30zi 374 Morpholine 87 130. 0 373 7. 5 170 mi. 188 Di-(2-ethy1hexyl)amine 241 130. 0 377 5. 5 166 32d 280 N-methylaniline 54 65 201 6. 0 167 33d 280 Di(beta-phenylethyhamine. 169 97. 5 295 6. 5 156 3411.. 280 Di-isopropanolamine.- 100 97. 5 272 4. 5 158 35d 280 Di-ethanolamine 79 97. 5 273 3. 0 156 -NOTE.I11 the above examples no catalyst Was added. In some duplications of the above small amounts of cata lyst were added up to 1% to 2% of either powered caustic soda or powdered sodium methylate. No advantage was noted in the use of a catalyst provided the amine was sufficiently basic.

In Examples 12d, 13d and 1403 indicated by the double asterisk the solvent was a mixture of 170 parts of henzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 14d and 15d Where the ratio was 1 to 3.5 to 1.75 in both instances.

In Examples 1d through 15d the resin employed was the one identified as Example 26a. In Examples 16d through d the resin employed was the one identified as Example 29a, and in Examples 26d through d the resin employed was identified as Example 36a.

as 26a and had a molecular weight of approximately 600. 175 grams of this resin were dissolved in slightly more than an equal weight of xylene and 61 grams of di-isopropanolamine added. 52 grams of alpha-gammadimethyl alpha methoxymethyl glutaraldehyde were added and the mixture stirred for about 35 minutes and then the temperature allowed to rise to approximately 140 C. or slightly higher, where it was allowed to re flux for 6.50 hours. During this refluxing period a phaseseparating trap was used to remove the water of formation. At the end of this time the reaction was complete and the product was obtained in the form of a xylene solution. A small sample was evaporated to eliminate the xylene. The resultant product was a rather hard somewhat tacky material, being reddish black in color.

Similar products were prepared as indicated in the following table:

TABLE V Alpha gamma dimethyl Solvent Max.

Resin Amt, alpha (xylene un- Time temp. Ex. No. amt, Secondary amine grams methoxy less otherperiod, during grams methyl Wise noted), hrs. reaction,

glutargrams C. aldehyde,

grams 175 Di-isopropanolamine 61 52 172 6. 5 146 150 Di-n-butylamine- 65 43 163 6. O 158 150 Dl-ethylamine 37 43 154 5. 5 142 150 Dr-eyclohexylamine. 91 43 158 6.. 5 162 300 Mprpholine 87 86 300 7. 0 147 300 Dr-2-ethylhexylamine 241 86 293 5. 0 165 225 B1s:(1,3-dimethylbutyl) amin 139 65 238 225 Di-lsopropanolamine 100 65 227' 4. 0 162 225 Alpha methylbenzyl eth 124 65 238 3. 5 156 lamina.

225 Diethanolamine 79 65 225 2. 5 159 225 Aminoethyl ethanolam 78 65 233 2. 5 143 225 Diethanolamine 79 65 -170 2. 5 102 225 o 79 55-170 3.0 225 do 131. 5 **55170 3. 5 101 225 Dl-isopropanolam 174 115 240 2. 0 128 236 Di-isopropylamine. 61 52 228 6. 5 144 197 Di-n-butylamine 65 43 195 5. 5 156 197 37 43 206 6.0 143 197 91 43 188 6. 5 162 393 97 86 389 7.0 393 241 86 396 5. 5 166 197 N-methylaniline 54 43 107 4. 5 168 TABLE V-Continued Alpha gamma dimethyl Solvent Max. Resin Amt, alpha (xylene un- Time temp. Ex. No. amt, Secondary amine grams methoxy less otherperiod, during grams methyl wise noted) hrs. reaction,

glutargrams C. aldehyde grams 295 Di(beta-phenylethyl) amine 169 65 303 4.0 158 295 Di-isopropanolamine 100 65 195 3. 5 153 225 Di-ethanolamine 79 65 300 2. 75 157 188 Di-isopropylaminc. 61 52 225 7 5 142 188 Di-n-butylamine 65 43 181 6. 160 188 Diethylamine 37 43 177 5. 142 374 Dl-cyclohexylamlne- 91 43 199 6. 5 160 374 Morpholine 87 86 375 7. 0 156 188 Di-(Zethylhexybam 241 86 375 5. 0 166 280 N-methylaniline 54 43 193 4. 5 172 280 Di (beta-phenylethyl) amine. 169 65 293 5. 0 160 280 Di-lsopropanolamine 100 65 275 3. 5 158 280 Di-ethanolamlne 79 65 273 3. 0 160 NOTE.-In the above examples no catalyst was added. In some duplications of the above small amounts of catalyst were added up to 1% to 2% of either powdered caustic soda or powdered sodium methylate. No advantage was noted in the use of a catalyst provided the amine was sufficiently basic.

In Examples 12a, 13e, and 14s indicated by the double asterisk the solvent was a mixture of 170 parts of benzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 142 and 15e where the ratio was 1 to 3.5 to 1.75 in both instances.

In Examples 1e through 15e the resin employed was the one identified as Example 26a. In Examples l6e through 2512 the resin employed was the one identified as Example 29a, and in Examples 26e through e the resin employed was identified as Example 36a.

Returning now to a consideration of the structure of the condensate it becomes obvious that one could obtain ring compounds. Using the abbreviated formula previously applied, the simplest ring could be shown thus:

Obviously, one could have rings with a larger number of members in the ring to say nothing of complications involving alkanol radicals, for instance, the elimination of a hydrogen atom from the alkanol hydroxyl group. Furthermore, the situation becomes even more complicated if the ratios are changed to correspond to ratios described in my co-pending application, Serial No. 376,- 240, filed August 24, 1953. In this particular instance there are described a number of complicated condensates in which 3 /2 moles of diethanolamine, or the like, 3 /2 moles of formaldehyde, and one mole of the phenolaldehdye resin, are employed. If corresponding condensates are prepared, replacing 3 /2 moles of formaldehyde by 1% moles of glyoxal pyruvic aldehyde, alphahydroxyadipaldehyde, and alpha-gamma-dimethyl-alphamethoxymethylglutaraldehyde, a variety of compounds are obtained which have unusual structure but are still organic solvent-soluble and susceptible to oxyalkylation. Indeed, another variety of somewhat more complicated materials are obtained by using as the amine reactant di(hydroxyethyl)N,N-ethylene diamine having the following structure:

HO C2114 H ounoH An initial product can be made treating the amine as it it were nothing more than a hydroxylated monoamine. Subsequently glyoxal may be added up to, for example,

the amount originally employed with the production of linear polymers and in some instances cross-linking, It is understood that regardless of what amine is used the final product obviously is, and must be, organic solventsoluble. The primary objective is to obtain a condensate which is organic solvent-soluble and not an infusihle resin. Such condensate is particularly valuable for oxyalkylation. The products so obtained find utility in various arts.

PART 4 At the present time there are available a number of alkylene oxides, particularly ethylene oxide, propylene oxide and butylene oxide, either as a single isomer or as a mixture of isomers. Glycide is available, or readily prepared. The same applies to methylglycide.

Oxyalkylation with any of the aforementioned alkylene oxides is comparatively simple in light of present day knowledge. In fact, it is stated briefly in US. Patent No. 2,636,038, dated April 21, 1953, to Brandner, in the following language: The compounds are prepared by the addition reaction between alkylene oxides and substitued oxazolines of the group named hereinbefore. The addition reaction is advantageously carried out at elevated temperature and pressure and in the presence of an alkaline catalyst.

As to a more complete description of oxyalkylation procedure reference is made to US. Patent 2,629,706, dated February 24, 1953, to De Groote and Keiser. See particularly the subject matter which appears in column 7 of said patent.

Propylene oxide and butylene oxide react somewhat more slowly than ethylene oxide and may require a somewhat higher temperature, somewhat greater agitation, or an increased amount of alkaline catalyst, such as finely powdered sodium hydroxide or sodium methylate. If the product to be subjected to oxyalkylation is xylene-soluble or soluble in any one of a number of inert solvents, there is no particular difficulty involved. The same is true if the product is a liquid at oxyalkylation temperatures. If it is not soluble or a liquid then in some cases initial oxyalkylation can be accomplished by means of an alkylene carbonate, such as ethylene carbonate or propylene carbonate which has a solubility eifect as well as acting as an oxyalkylation agent. As soon as a suitable product is obtained by the use of a carbonate, further reaction can be completed with the oxide. An alternate procedure sometimes employed with insoluble materials is to reduce the products to an extremely finely ground powder and oxyalkylate during suspension using particularly vigorous agitation.

All these procedures have been described repeatedly in the literature and, as a matter of fact, suitable operational directions are available from any one of several makers of alkylene oxides.

Example If Due to their ready availability, the bulk of the oxyalkylation derivatives were prepared from ethylene oxide, propylene oxide, butylene oxide, or a mixture of the same. Generally speaking the autoclaves or oxyalkylators employed ranged from approximately 2 gallons in size to approximately 20 gallons in size. The general procedure was to start with a fairly small sample; for instance, approximately 2000 grams, of the product to be oxyalkylated and 1000 grams of a solvent such as xylene, or a high-boiling anomatic solvent, or the diethylether of ethylene glycol, or a mixture of these solvents. Powdered caustic soda, or sodium methylate, was added as a catalyst in an amount generally not over 2%, and more catalyst was added if the amount dropped to /z% or less. Initial oxyalkylation generally started by adding 50% by weight, 100% by weight, 200% by weight, 300% by weight, 500% by weight, etc., until at least ten times as much oxide had been added, at least in some examples. Excellent compounds or suitable raw materials have been obtained by adding as much as 50 parts by weight of oxide to one part of the initial reactant. In some instances the same examples were repeated and then reacted with one or more oxides; for instance, in the tables which follow there are examples where an oxyethylated product was oxypropylated subsequently, or vice-versa. Comparatively small samples, for instance, one to five grams, were taken at various stages and tested for emulsifiability factor and also for demulsifying efiect on crude oil emulsions. The tabular data do not reflect the slight discrepancy due to sample withdrawal.

More specifically then, 15 pounds (6,500 grams) of the condensate previously identified as Example 1b, were mixed with an equal weight of solvent (being xylene in this series). The mixture was placed in a small autoclave together with one-half pound of finely powdered caustic soda, and stirred, and the temperature raised to approximately 130 C. 2 pounds (1135 grams) of ethylene oxide were added in approximately 15 minutes. The pressure during the oxyalkylation was about to pounds per square inch. The resultant product was a fluid having a reddish black cast. Except for the withdrawal of a few grams for examination, the product was then subjected to further oxyalkylation with another 2.5 pounds of ethylene oxide and without the addition of any more catalyst or any more solvent.

Note what is said in regard to these examples and subsequent examples in the text immediately following, and in the tables.

A number of additional examples appear in tabular form in the twenty tables immediately following, to wit, Tables VI through XXV. These are self-explanatory, particularly in regard to the first three tables of each series of five. The last two require a little more careful examination. This is due to an effort to condense the data and not burden the text with an unduly large volume of detail.

Due to the fact that various size quantities are used the ratios sometimes appear in grams or kilograms and sometimes in pounds. When pounds are used the designation is included.

In Tables VI, VII and VIII, XI, XII and XIII, XVI, XVII and XVIII and XXI, XXII and XXIII, successive stages of oxyalkylation are shown. Small samples of a few grams were withdrawn and tested for solubility and also for demulsification effectiveness. The withdrawal of such small samples was ignored. In some instances the example was repeated and used subsequently for reaction with one or more other oxides. In some instances the product so obtained in the first stage of oxyalkylation represented a comparatively large quantity and was subdivided perhaps into one-half or even a smaller fraction, and then this smaller fraction only subjected to oxyalkylation with another oxide. As previously noted, no further explanation is required in regard to the first three tables of each series of five. In the fourth table of each series, i.e., Tables IX, XIV, XIX, and XXIV, for example in 18 Table IX, it is to be noted that Example 11 is derived from Example 8 Referring to Example 8f it will be noted this was derived originally from oxyalkylation-susceptible compound Example 1b. In Example 8f, oxyalkylationsusceptible compound Example 112 had already been treated with ethylene oxide. Thus, in Table IX, although the oxyalkylation-susceptible compound is properly designated as Example 8] for the reason it is now the reactant subjected to oxypropylation, the oxyalkylation-susceptible compound as far as reference to weight goes (in this instance 7 /2 pounds) goes back to the original compound Example 1b. This is obvious, and is even more obvious for the reason that it is subsequently emphasized in connection with the weight ratio, as explained subsequently.

It will be noted also that in the fourth column in Table 1 IX the oxide used is marked as indicated and in each instance the oxide employed in this second stage is shown, in two instances in Table IX being propylene oxide and in one instance being ethylene oxide.

Bearing in mind what is said in regard to Example 1i being derived from Example 8 1, which in turn was derived from Example 112 plus ethylene oxide, it should be noted that this table does not, as far as the first four columns go, reflect the amount of oxide which was: added in the initial or earlier stage. As previously noted, this does not cause confusion and, in fact, permits holding the data to a minimum in light of what is said next.

Referring now to columns seven, eight, nine and ten which are concerned with composition at the end, it will be noted that these data do take into consideration the amount of oxide added initially as well as the oxide during the second stage. Thus, although this shows the propylene oxide added it also shows the original ethylene oxide as representing the five-to-one weight ratio based on the oxyethylation of the first stage. This can be stated perhaps more simply in the following way: On initial examination the table shows that Example It was derived from Example 8 As to the composition of Example 8 one need only note that in the seventh column it shows that 7 /2 pounds of propylene oxide were added and the weight ratio to the oxyalkylation-susceptible compound Example 1b was one-to-one, but it also shows that the weight ratio of the ethylene oxide at the same stage was five-to-one. Thus, without even checking back to a prior table it is obvious the initial material, Example 8f, subjected to a second .oxyalkylation step, consisted of a product in which one part of the oxyalkylation-susceptible compound was combined with 5 pounds by weight of ethylene oxide, prior to oxypropylation.

All the data in Table IX, X, XIV, XV, XIX, XX, XXIV and XXV are presented in the same way. We find this is the 'most simple and concise tabular presentation that yet has been developed after a considerable series of experimentations, and reports in table form. This is true even where three oxides were employed as for instance in Example 1 in Table X. Example 1 j was obtained from Example 3i in Table IX. Example 3i as indicated, was obtained by an oxypropylation of Example 11, and Example li, as previously noted, was obtained from Example 8f. The preparation of Example 8] from Example lb has been discussed in considerable detail in the previous text. Again it is to be noted that in the tables the ratios of the oxide to the initial product prior to oxyalkylationis shown so there is no question as to the composition of each example although considerable data have been presented in what is a comparatively condensed and readily understandable form.

Note what is said in regard to the color of the products in the tables. For most industrial purposes there is no objection to the color. The products can be decolon'zed by conventional procedure, using bleaching earths, filtering clays, charcoal, or the like. A trace or small amount of catalyst, if present, can be removed for most purposes by the mere addition of a comparable amount of hydrochloric acid or by any other suitable means.

TABLE VI Composition before-Amount of OSC, catalyst anid solvent constant before and after oxyalkyl- Composition at end Operating conditions at on Ex Weight ratio End product- N Color and physical OSC Oxide Cata- Xylene Oxide Max. Max. Time state Ex. OSC 1 used, lyst, solvent, used, EtO to H0 to BuO to pres., temp., of re- No. grams EtO, NaOH, grams EtO, oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams grams grams 9 ation ation ation hrs.

snscept. suscept. suscept.

cmpd. cmpd. ompd.

15# 0 0. 2. 5# 130-135 M Reiddiish black u1 15 2. 5 0.5 15 5. 0 130-135 14 Do. 15 5.0 0. 5 15 7. 5 130-135 Do. 15 7. 5 0.5 15 15.0 130-135 Viscous liquid. 15 15.0 0.5 15 30.0 130-135 1% D0. 15 30.0 0.5 15 45. 0 130-135 2 Very viscous. 15 45. 0 0.5 15 60.0 130-135 2 o. 15 60. 0 0. 5 15 75.0 130-135 2% Semi-solid to Greasy consist. 0 1. 0 30 7. 5 -135 Reiddtiish black u1 30 7. 5 l. 0 30 15. 0 0. 130-135 Do. 30 15.0 1. 0 30 30.0 1.0 130-135 1% Viscous liquid. 15.0 15.0 0. 5 15 30. 0 2. 0 130-135 1% Do. 15.0 30.0 0. 5 15 45. 0 3.0 130-135 2 Very viscous. 14f 13f 15.0 45. 0 0.5 15 52. 5 3. 5 130-135 2% Do. 15f 14f 15.0 52. 5 0.5 15 60.0 4.0 130-135 2% Semi-solid.

1 Oxyalkylation-suseeptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE VII Composition beioreAmount of 080, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation Ex. Weight ratio End product- No. Color and physical OSC 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. OSC used, PrO, lyst, solvent, used, PrO, EtO to H0 to BuO to pres, temp., of re- No. grams grams N aOH, grams grams oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

25. 0# 0 2. 5# 25. 0# 50. 0# 2. 0# 130-135 6 Greenish black viscous liquid. 12. 5 25.0 1. 25 12. 5 50.0 4.0 130-135 2% Do, 12.5 50.0 1. 25 12. 5 75.0 6.0 130-135 2% Do 6. 25 37. 5 .625 6. 25 50. 0 8. 0 130-135 2 D0 6. 25 50.0 .625 6. 25 75.0 12.0 130-135 3 Do 6. 25 75.0 .625 6. 25 87. 5 14.0 130-135 2% D0 3. 0 42.0 .3 3.0 54. 0 18. 0 130-135 2% Do 3.0 54.0 3 3.0 75.0 25.0 130-135 3% Do 20.0 0 2.0 20.0 60.0 3.0 130-135 6 Do 15.0 45. 0 1. 5 15.0 70.0 4. 67 130-135 2 Do 10.0 46. 67 1. 0 10.0 60. 0 6.0 130-135 1% Do 10.0 60. 0 1.0 10.0 80.0 8.0 130-135 2 Do 5.0 40. 0 5 5.0 60. 0 12.0 130-135 2% Do 5.0 60.0 .5 5.0 90. 0 18.0 130-135 3% Do. 15g--. 14g 2. 5 45. 0 .25 2. 5 62.0 24.8 10-15 130-135 3 Do.

1 Oxyalkylation-suseeptible compound. 4 2 In some instances weights change from gram basis to pound basis. Such change 1n unit is obvious.

TABLE VIII Composition before-Amount of 080, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation Ex. Weight ratio End product- No. Color and physical OXlde Oata- Oxide Time state OSC 1 OSC 1 used, lyst. Xylene used, EtO to PrO to BuO to Max. Max. of re- Ex. grams BuO, NaOH, solvent, BuO, oxyalkyloxyalkyloxyalkylpres, temp., action, No. grams grams grams grams 2 ation ation ation p.s.i. 0. hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

10. 0# 0. 0# 1. 0# 10. 0# 10. 0# 1. 0 20-35 -145 2 Black viscous li uid. 10.0 10.0 1.0 10. 0 20.0 2.0 20-35 135-140 2% Do. 10.0 20.0 1. 0 10.0 30.0 3.0 20-35 130-135 3% Do 10.0 30.0 1.0 10.0 40. 0 4.0 20-35 130-135 3% Do 10.0 40.0 1. 0 10.0 50.0 5.0 20-35 130-135 3% Do 25.0 0.0 2. 5 25.0 25.0 1.0 20-35 -145 3 Do 25.0 25.0 2. 5 25.0 50.0 2.0 20-35 130-135 Do 12.5 25.0 1. 25 12.5 37. 5 3.0 20-35 130-135 2% Do 12. 5 37. 5 1. 25 12. 5 50. 0 4. 0 20-35 130-135 Do 12.5 50.0 1. 25 12.5 75.0 6.0 20-25 130-135 3% Do 20.0 0.0 2.0 20.0 20.0 1. 0 20.35 130-135 3% Do 20.0 20. 0 2.0 20.0 40.0 2. 0 20-35 130-135 Do 20.0 40.0 2.0 20.0 60.0 3.0 20-35 130-135 3% Do 10.0 30.0 1.0 10.0 50.0 5.0 20-35 130-135 3% Do. 10.0 50.0 1.0 10.0 75.0 7. 5 20-35 130-135 4% Do 1 oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious,

TABLE IX Composition before-Amount of CS0, catalyst and solvent constant before and after oxyaikyl- Composition at end Operating conditions ation End productg; Welght who Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, as lyst, solvent, used, as EtO to PrO to BuO to pres., temp., of re- No. grams indicated, N aOH, grams indicated, oxyalkyloxyalkyloxyalkylp.s.i. C. action,

grams grams grams 1 ation ation ation hrs.

suscept. suscept. suscept crnpd. crupd. crnpd. 7. 5# #Pr0 .75# 7. 7. 5#Pr0 5.0 1.0 -15 130-135 A Reddish black,

semi-fluid. 7. 5 7. 5 .75 7. 5 15. 0 5. 0 2.0 10-15 130-135 Do. 7. 5 15. 0 75 7. 5 37. 5 5. O 5. 0 10-15 130-135 1 Do. 7. 5 37. 5 75 7. 5 52. 5 5. 0 7.0 10-15 130-135 2 Do. 3. 75 26. .375 3. 75 56. 5. 0 15. 0 10-15 130-135 4 Do. 5. 0 0#Et0 0. 5 5. 0 10#Et0 2.0 8.0 10-15 130-135 V G reenish black viscous liquid. 5. 0 10.0 0. 5 5. 0 20.0 4.0 8.0 10-15 130-135 Do. 5. O 20.0 0. 5 5. 0 40.0 8. 0 8.0 10-15 130-135 1 Do. 5. 0 40.0 0.5 5.0 50.0 10.0 8.0 10-15 130-135 1 Do. 5. 0 50. 0 0. 5 5. 0 60.0 12.0 8.0 10-15 130-135 1% Do. 10. 0 0#Pr0 1. 0 10. 0 30. 0#Pr0 3.0 5. 0 10-15 130-135 2 Black viscous iquid. 10. 0 30.0 1. 0 10. 0 60.0 6.0 5. 0 10-15 130-135 2 Do. 5. 0 30. 0 5 5. 0 50. 0 10. 0 5. 0 10-15 130-135 2% Do. 5. 0 50. 0 .5 5. 0 80. 0 16.0 5. 0 10-15 130-135 3% D0. 2. 5 40. 0 25 2. 5 60. 0 24.0 5. 0 10-15 130-135 3% D0. 1 Oxya1ky1ation-susceptible compound. 2 In some instances Weights change from gram basis to pound basis. Such change in unit is obvious. 3 Weight ratio based on original oxyalkylation-susceptible compounds prior to any oxyalkylation.

TABLE X Composition before-Amount of OSC, catalyst A and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation 7 End product- 5 Welght Color and physical 050 1 Oxide Cata- Xylene Oxide M Max. Max Time state Ex. 050 1 used, as lyst, solvent, used, as EtO to FIG to BuO to pres., temp of re N 0. grams indicated, NaOH, grams indicated, oxyelkyloxyalkyloxyalkylp.s.i. C. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpd. cnipd. cmpcl. 750 OBuO 75 750 37513110 5 5 0. 5 -65 135-145 2 Reddish black viscous liquid. 750 375 750 750 5 5 1. 0 60-65 135-145 2% Do. 750 750 75 750 1, 500 5 5 2. 0 60-65 135-145 5 Do. 375 750 37. 5 375 1, 500 5 5 4.0 60-65 135-145 3% Do. 375 1, 500 37. 5 375 1, 875 5 5 5. 0 60-65 135-145 4 Do. 500 013110 50 500 500Bu0 12.0 8. O 1.0 60-65 135-145 2% Greenish black vis. 1i uid. 250 250 25 250 500 12.0 8.0 2.0 60-65 135-145 2 IDo. 250 500 25 250 750 12. 0 8. 0 3. 0 60-65 135-145 3 Do. 125 375 12. 5 125 625 12. 0 8. 0 5. 0 60-65 135-145 4 Do. 125 625 12. 5 125 1, 000 12.0 8.0 8. 0 60-65 135-145 5 Do. 250 OEtO 25 250 25EtO 1.0 24. 0 5. 0 10-15 125-130 1 Black to dark amber vis. liq. 250 250 25 250 500 2. 0 24. O 5. 0 10-15 125-130 1% D0. 125 250 12. 5 125 500 4. 0 24. 0 5. 0 10-15 125-130 1% Do. 125 500 12.5 125 1,000 8.0 24.0 5. 0 10-15 125-130 3% Dark anber vis.

liqui 15j 14 125 1,000 12.5 125 1, 500 12.0 24.0 5. 0 10-15 125-130 4 Do.

1 Oxyalkylation-susceptiblc compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious. 3 Weight ratio based on original oxyalkylation-susceptible compounds prior to any oxyalkylation.

TABLE XI Composition before-Amount of OSC, catalyst and solvent constant before and after oxyalkyl- Compositlon at end Operating conditions ation End product- Welght ram) Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 030 1 used, lyst, solvent, used, EtO, EtO to PrO to B to pres., temp., of re- No. grams EtO, NaOH, grains grams 2 oxyalkyloxyalkyloxyalkylp.s.i. C. action,

grams grams ation ation ation hrs.

suscept. cmpd. 15. 0# 0 675 15. 0# 5. 0# 0.33 -130 Dlark amber vis.

iq. 15. 0 5. 0 675 15. 0 10. 0 .67 125-130 Do. 15. 0 10.0 675 15. 0 l5. 0 l. 0 125-130 55 D0. 15. 0 15. 0 675 15.0 20. 0 1. 33 125-130 A Do. 15. 0 20. 0 675 15. 0 30.0 2.0 125-130 1% Very viscous. 15.0 30.0 675 15.0 45.0 3.0 125-130 1% Heavy viscous.

7.5 22. 5 337.5 7.5 30.0 4.0 125-130 1% Semi-fluid. 7. 5 30. 0 337. 5 7. 5 45.0 6.0 125-130 1% o. 30.0 0 450 30.0 5. 0 0.167 125-130 Gree'nish black vis. liq. 30.0 5. 0 450 30.0 10. 0 0.333 125-130 A Do. 30. 0 10. 0 450 30.0 15. 0 0.50 125-130 Do. 30.0 15. 0 450 30. 0 30. O 1.0 125-130 1 Do. 15. 0 15. 0 225 15. 0 30. 0 2.0 125-130 1 Very viscous. 15. 0 30. 0 225 15. 0 45.0 3.0 125-130 1% D0. 15. 0 45. 0 225 15. O 60.0 4. 0 125-130 1% Semi-fluid. 1 Oxyalky aticn-susccptible compound.

2 111 some instances weights change from gram basis to pound basis.

Such change in unit is obvious.

TABLE XII Composition before-Amount of OSC, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation Ex Weight ratio End product N Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 050 1 used, lyst, solvent, used, EtO to PrO to pres, temp, of re- No. grams PrO, NaOH, grams PrO, oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams grams grams 2 ation ation hrs susccpt. suscept. cmpd. cmpd.

1121... 11c 15. 0# 0# 675 15. 0# 30. 0# 2.0 2 Dialrlgd amber vis.

ui 2m..- km... 15.0 30.0 675 15.0 60.0 4. 0 2% Do 3m-.- 2m 10.0 40.0 450 10.0 80.0 8.0 3% Do. 4m. 3m 5. 0 40. 0 225 5.0 75. 0 15. 0 3% D0. 5m... 4m 5.0 75.0 225 5.0 90.0 18. 0 3 Do. 6m 5m 2. 5 45.0 113 2. 5 50.0 20.0 2 Do. 7m 6m 2. 5 50.0 113 2. 5 70. 0 28.0 2% D0. 8m..- 7m 2. 5 70.0 113 2. 5 75.0 30.0 2% Do. 9m. 160---. 20.0 0.0 900 20. 0 60. 0 3. 0 3% Do. 10711.-- 9m 10.0 30.0 450 10.0 60.0 6.0 2% Do. 1111!... 10m 10.0 60. 0 450 10. 0 90.0 9.0 2% Do. 12121-. 11m 5.0 45.0 225 5.0 90. 0 18.0 4 Do. 13m 12m- 4.0 72.0 180 4. 0 80.0 20.0 2 Do. 14m 13m. 4.0 80.0 180 4.0 100.0 25.0 3% Do. 1577!... 14m 2.0 50.0 2.0 64. 0 32.0 3 Do.

1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

' TABLE XIII Composition beforeAmount of OSC, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation Ex Weight ratio End product Color and physical OSC 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. OSO 1 used, BuO, lyst, solvent, used, BuO, EtO to PrO to pres., temp., of re- No. grams grams NaOH, grams grams 2 oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams ation ation hrs.

suscept. suscept. cmpd. cmpd.

30. 0# 0. 0# 450 30. 0# 30. 0# 1.0 10-15 135-145 4% Black vis. liq. 20.0 20.0 300 20.0 40. 0 2.0 10-15 135-145 2A Do. 20.0 40.0 300 20.0 60.0 3. 0 10-15 130-135 2% Do. 15.0 45.0 225 15.0 60. 0 4.0 10-15 130-135 2% Do. 10.0 40.0 150 10.0 50.0 5.0 10-15 130-135 3 Do. 40.0 0.0 675 40. 0 20.0 5 10-15 135-140 2% Reddish black vis.

1(1. 30.0 15.0 450 30.0 30.0 1.0 10-15 130-135 2% Do. 30.0 30.0 450 30.0 45. 0 1. 5 10-15 -130 3 Do. 15.0 22. 5 225 15.0 30. 0 2.0 10-15 125-130 2 Do. 15.0 30.0 225 15.0 60.0 4.0 10-15 125-130 5 Do. 20.0 0.0 675 20.0 40. 0 2.0 10-15 -135 5 Dark amber vishq 20.0 40. 0 675 20.0 60. 0 3.0 10-15 125-130 3 Do. 10.0 30.0 338 10.0 60.0 6.0 10-15 125-130 4 Do. 5.0 30.0 169 5.0 50.0 10.0 10-15 125-130 3 D0. 15'n. 1411.... 5.0 50.0 169 5.0 100.0 20.0 10-15 125-130 0% Do.

1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE XIV Composition before-Amount of 080, catalyst and solvent constant before and after oxyalkyl- Composltion at end Operating conditions ation Ex Weight ratio End product- Color and physical 050 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. OSC 1 used, as lyst, solvent, used, as EtO to PrO to pres, temp, of re- No. grams indicated, N aOH, grams indicated, oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams grains grams 2 ation ation hr suscept. suscept. cinpdfi cmpd.

2, 250 OBuO 225 2, 250 1, 12513110 3.0 1% Dark amber heavy vis. liq. 2,250 1,125 225 2,250 2,250 3.0 1% Vi li 1,125 1,125 112. 5 1,125 2,250 3. 0 2% D 1,125 2,250 112.5 1,125 3, 375 3.0 3 D 675 2, 025 67.5 675 750 3. 0 6 500 OEtO 50.0 500 250Et0 0.5 18.0 D 500 250 50. 0 500 500 1.0 18. o 500 500 50.0 500 1, 500 3.0 18.0 1 D 250 750 25.0 250 1,500 6. 0 18. 0 1% D 250 1, 500 25.0 250 ,000 8.0 18.0 1% D 1,125 OPrO 85.0 a. 0 2 2 D 750 2,250 85. 0 5.0 2% D 750 3, 750 85. 0 10.0 4% D 14p 375 3,750 42. 5 15.0 3 D 15p 1411.. 375 5, 625 42. 5 20.0 3% D 1 Oxyalkylation-susceptible compound.

1 In some instances weights change from gram basis to pound basis.

3 Weight ratio based on original oxyalkylation-suscep 25 26 TABLE XV Composition before-Amount of 080, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation EX Weight ratio End product N Color and physical 03C 1 Oxide Cata- Xylene Ox1de Max. Max. Time state Ex. 0S0 1 used, as lyst, solvent, used, as EtO to PrO to B110 to pres, temp, of re- N 0. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpdfi cmpd.

675 OPrO 67. 675 3, 375Pr0 3.0 5.0 10.0 -15 125-135 6 Dark amber vis.

liq.

202. 5 2, 430 20. 202. 5 3, 0'37. 5 3. 0 15. 0 l0. 0 10-15 125-135 2% Do.

250 013110 25. 0 250 125E110 8. 0 18. 0 0. 5 10-15 125-135 2 Do.

375 013130 42. 5 375 375Et0 1. 0 20. 0 20. 0 10-15 125-135 1 D0.

250 400 28. 5 250 500. O 2. 0 20. 0 20. 0 10-15 125-135 1 Very viscous. 250 500 28. 5 250 750. 0 3. 0 20. 0 20. 0 10-15 125-135 1% D0.

1 Oxyalkylation-susceptiblc compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious. 3 Weight ratio based on original oxyalkylation-susceptible compounds prior to any oxyalkylation.

TABLE XVI Composition before-Amount of 080, 1 catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation EX Weight ratio End product- N Color and physical OSC Oxide Cata- Xylene Ornde Max. Max. Time state Ex. 080 1 used, lyst, solvent, used, Eto, EtO to PrO to BuO to pres, temp, of re- No. grams EtO, NaOH, grams grams 2 oxyaikyloxyalkyloxyalkylp.s.i. 0. action,

grams grams ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

Oxyalkylation-susceptible compound.

2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

3 Reddish black vis. liq. in examples in this series the color became somewhat lighter but viscosty increased until the last sample was a solid of semi-solid.

TABLE XVII Composition beforeAmount of 08C, 1 catalyst and solvent constant before and alter oxyalkyl- Composition at end Operating conditions ation E Weight ratio End produet- Color and physical OSC Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, lyst, solvent, used, EtO to PrO to BuO to pres, temp., of re- N 0. grams PrO, N 21011, grams PrO, oxyalkyloxyalkyloxyalkyl p.s.i. C. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

21. 0# 01 900 20.0# 42. 01? 2.0 4% Reddish black vis.

liq.

21.0 42.0 900 20.0 84.0 4.0 5 Do. 10.5 42. 0 450 10.0 84. O 8.0 5 D0. 5. 25 42.0 225 5.0 63. 0 12.0 3 D0. 5. 25 63. O 225 5.0 78. 75 15.0 4 Do. 3.15 47. 25 3.0 57.0 18.1 3 D0. 3.15 57. 0 135 3.0 78.75 25. 0 5% D0. 3.15 78.75 135 3.0 88.0 27. 9 4 Do. 16.0 0 720 14.0 70.0 4. 37 6% D0. 8.0 35.0 360 7.0 85.0 10.62 5 Do. 4.0 42. 5 180 3. 5 72.0 18.0 3% D0. 4.0 72.0 180 3.5 85.5 21.4 2% D0. 2.0 42.75 90 1.75 50.0 25.0 1% Do. 2. 0 50. 0 90 1. 75 56.0 28.0 2 Do. 15s 148.... 2.0 56.0 90 1. 75 60.0 30.0 25-30 2 Do.

1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE XVIII Composition beioreAmount of OSC, 1 catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation Weight ratio End product- 113x. Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, BuO, lyst. solvent, used, BuO, EtO to PrO to BuO to pres., temp., of re- No. grams grams NaOH, grams grams 2 oxyalkyloxyalkyloxyalkylp.s.i. C. action,

grams ation ation ation hrs.

suscept suscept suscept. cmpd. cmpd. cmpd.

1t- 20d 35. 0# 675 30. 0# 17# 485 25-30 130-135 2% Gllcenish black vis.

lq. 35. 0 17. 0 675 30. 0 1. 0 25-30 130-135 2% Do. 17. 17. 5 337. 5 15.0 1. 5 25-30 130-135 2 Do. 17. 5 26. 25 337. 5 15. 0 2. 0 25-30 130-135 2 Do. 17. 5 35. 0 337. 5 15. 0 2. 46 25-30 130-135 3 Do. 18.0 0 810 18.0 1. 0 25-30 130-135 2% Dark amber to black vis. liq. 18. 0 18. 0 810 18. 0 2. 5 25-30 130-135 4% Do. 18.0 45. 0 810 18. 0 3.0 25-30 130-135 2 D0. 9. 0 27.0 405 9. 0 4. 2 25-30 130-135 2% Do. 9. 0 37. 8 405 9. 0 5. 5 25-30 130-135 3 Do. 21.0 0 495 23.0 9 25-30 130-135 3 Dill: zllimber to c 21. 0 18.9 495 23.0 1. 2 25-30 130-135 1% Vis. liq. 21. 0 25. 2 495 23. 0 2. 5 25-30 130-135 5 Do. 11. 5 26. 25 247. 5 11. 5 3. 7 25-30 130-135 4 Do. L- 11. 5 42. 5 246. 5 11. 5 5. 0 -30 130-135 4 Do.

1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE XIX Composition beforeAmount of 080, 1 catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation EX Weight ratio End product- N Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. OSO 1 used, as lyst, solvent, used, as EtO to PrO to 13110 to pres, temp., of re- No. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept suscept. cmpd. ompd. cmpd.

3 0 kg. 0kg. BuO 300 2.0 kg. 1. 0 kg. 4.0 .33 25-30 125-130 1% Reddish bl. heavy BuO vis. liq. 3.0 1. 0 300 2.0 2.0 4.0 .67 25-30 125-130 1% Vis. liq. 3.0 2. 0 300 2. 0 3.0 4.0 1. 0 25-30 125-130 2 Do. 3.0 3.0 300 2. 0 4. 5 4.0 1. 5 25-30 125-130 2% D0. 3.0 4. 5 300 2.0 12.0 4.0 4.0 125-130 8% D0. 1. 0 OEtO 100 1.14 1. OEtO 1. 0 18.0 125-130 Do. 1. 0 1. 0 100 1.14 1.3 1.3 18. 0 125-180 Do. 1. 0 1. 3 100 1.14 2. 4 2. 4 18.0 125-130 1% Do. 1. 0 2. 4 100 1.14 4.0 4.0 18.0 125-130 1% Do. 1. 0 4.0 100 1.14 9. 6 9. 6 18.0 125-130 5 D0. 1.28 OPrO 130 1.28 6. 4PrO 5.0 5.0 125-130 2% Dk. amber vis. liq. 23 4 1 1- 8 12- 8 10.0 5. 0 125-130 2% Do. 64 6. 4 64 10. 0 15. 6 5. 0 125-130 2 D0. 64 10. 0 65 64 12. 8 20.0 5. 0 25-30 125-130 1 Do. 15a-.- 14u 64 12.8 65 64 14.1 22. 0 5. 0 25-30 125-130 1% Do.

1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis topound basis. Such change in unit is obvious. 3 Weight ratio based on original oXyalkylation-susceptible compounds prior to any oxyaikylation.

TABLE XX Composition beforeAmount of 080, 1 catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation End productgi' Weight who Color and physical OSO Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, as lyst, solvent, used, as EtO to PrO to BuO to pres, temp, of re- No. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxya1kylp.s.i. 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept suseept. cmpd. cmpd. cmpd.

in... 5a..... 1. 5 kg. 0 kg. PrO 150 1. 0 kg. 6.0 kg. 4.0 4.0 4.0 25-30 125-130 3% Reddish black vis PrO. PrO. liq. 1. 5 6.0 150 1. 0 12. 0 4.0 8.0 4.0 25-30 125-130 3% D0. 6.0 75 .5 7. 5 4.0 10.0 4. 0 25-30 -130 D0. 75 7. 5 75 5 10. 5 4.0 14. 0 4. 0 25-30 125-130 1% Do. .75 10.5 75 5 12.0 4.0 16.0 4. 0 25-30 125-130 1% D0. 0. 5 0BuO 50 57 2. 013110 9. 6 18.0 4.0 25-30 125-130 3 Do. 0. 5 2.0 50 57 2. 8 9. 6 18.0 5. 6 25-30 125-130 1 Do. 0. 5 2. 8 50 57 3. 5 9. 6 18.0 7. 0 25-30 125-140 1 Do. 0. 5 3. 5 50 57 4. 8 9. 6 18.0 9. 6 25-30 125-130 2% Do. 0.5 4. 8 50 .57 5. 5 9. 6 18.0 11. 0 25-30 125-130 2 Do.

.64 013110 65 .64 .64Et0 1.0 15.6 5.0 25-30 125-130 44 Dark amber Vis.

i uid. 64 .64 65 64 1. 28 2.0 15. 6 5. 0 25-30 125-130 Do, 64 1. 28 65 64 1. 92 3.0 15. 6 5. 0 25-30 125-130 Do. 64 1. 92 65 64 2. 56 4. O 15. 6 5. 0 25-30 125-130 Do. 64 2. 65 64 3. 20 5. 0 15. 6 5. 0 25-30 125-130 4 Do,

1 Oxyalkylation-susceptible compound.

11 In some instances weights change from gram basis to pound basis.

Such change in unit is obvious.

TABLE XXI Composition before-Amount of 080, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions ation EX Weight ratio End product Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, lyst, solvent, used, EtO to PrO to BuO to pres, temp., of re- No. grams EtO, NaOH, grams EtO, oxyalkyloxyalkyloxyalkyl p.s.i. C. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

30.01? 450 16. 0# 7. 0.25 110-115 Dark amber vis.

liq. 30. 0 7. 5 450 16.0 15. 0 .50 110-115 Do. 30.0 15.0 450 16. 0 30. 0 1.0 110-115 Do. 30.0 30.0 450 16.0 45.0 1. 5 110-115 Do. 30.0 45.0 450 16.0 60.0 2.0 110-115 1 Do. 15.0 30.0 225 8.0 60.0 4.0 110-115 2 Dark amber very vis. liq. 7. 5 30. 0 112. 5 4.0 45.0 6. 110-115 1% Amber-greasy 7. 5 45. 0 112.5 4.0 60. 0 8. 110-115 2 Lt. amber solid. 12. 5 0 250 10.0 12. 5 1. 110-115 1% Rfddisclll black lqUl 1010.. 910.. 12.5 12.5 250 10. 0 25. 0 2. 110-115 1% Vis. liq. 1121)-- w--. 12.5 25.0 250 10. 0 31.2 2. 110-115 Do. 1210.. 1110... 12.5 31.2 250 10.0 37.5 3. 110-115 D0. 3112.. 12m... 12. 5 37. 5 250 10. 0 40. 0 3. 110-115 1 Do. 14w 1310". 12.5 40. 0 250 10. 0 50.0 4. 110-115 1% Very viscous. 15w 14w-.- 12.5 50.0 250 10. 0 56. 2 4. -115 1% Heavy to greasy.

1 Oxyalkylation-susceptible compound. 1 In some instances Weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE XXII Composition before-Amount of 080, catalyst and solvent constant before and after oxyalkyl- Composltion at end Operating conditions ation EX Weight ratio End product- N Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. OSC 1 used, lyst, solvent, used, EtO to PrO to B110 to pres, temp, of re- No. grams PrO, NaOH, grams PrO, oxyalkyloxyalkyloxyalkylp.s.i. C. action,

grams grams grams 2 atlon ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

11. 0# 0# 495 12. 0# 44. 0# 4.0 -125 5 Dark amber vis. liq. 11.0 44.0 495 12. 0 66.0 6.0 115-125 3 Do. 5. 5 33. 0 247. 5 6. 0 66. 0 12. 0 115-125 4% Do. 5. 5 66. 0 247. 5 6. 0 88. 0 16. 0 115-125 4 D0. 3. 3 52.8 148. 5 3. 6 59. 4 18.0 115-125 2 Do. 3. 3 59. 4 148. 5 3. 6 72. 6 22.0 115-125 2% Do. 3. 3 72.6 148. 5 3. 6 82. 5 25.0 115-125 2% Do. 3. 3 82. 5 148. 5 3. 6 92. 4 28.0 115-125 3% Do. 10. 0 0 450 10. 0 80. 0 8. 0 115-125 6. 0 Do. 5.0 40. 0 225 5.0 80.0 16.0 115-125 4.0 Do. 2. 5 40.0 112. 5 2. 5 50. 0 20.0 115-125 3 Do. 2. 5 50. 0 112.5 2. 5 60.0 24.0 115-125 3 Do. 2. 5 60.0 112. 5 2. 5 65.0 26.0 115-125 2% Do. 2. 5 65.0 112.5 2. 5 70.0 28.0 115-125 2% Do. 2. 5 70.0 112.5 2. 5 75.0 30.0 115-125 3 Do. 1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE XXIII Composition beforeAmount of OSC, cata1yst and solvent constant before and after oxyalky1- Composition at end Operating conditions ation Ex, Weight ratio End prodnct N o. Color and physical OSC 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, lyst, solvent, used, 131.0 to Pro to BuO to pres, temp., of re- No. grams BuO, N aOH, grams BuO, oxyalkyloxyalkyloxyallcylp.s.i. 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

4, 680 0 468 5, 740 5 25-30 -135 3% Dark amber vis. liq.

680 2, 340 468 5, 740 1. 0 25-30 130-135 3% Do. 680 4, 680 468 5, 740 1. 5 25-30 130-135 2 Do. 680 7, 020 468 5, 740 2. 0 25-30 130-135 2 Do. 2, 340 4, 680 234 2, 870 4. 0 25-30 130-135 5 D0. 10. 0# 0# 450 10. 5 1. 0 25-30 130-135 2% Do. 10. 0# 10. 0 450 10. 5 2. 0 25-30 130-135 2% Do. 10. 0 20.0 450 10. 5 4. 0 25-30 130-135 4 Do. 10. 0 40. 0 450 10. 5 6. 5 25-30 130-135 4% Do. 10. 0 65. 0 450 10. 5 8. 8 25-30 130-135 5 Do. 18. 5?! 0# 825 16. 5# 5 25-30 130-135 2 Do. 18. 5 9.25 825 16. 5 1. 0 25-30 130-135 2% D0. 18. 5 18.50 825 16. 5 1. 8 25-30 130-135 4 Do. 18. 5 33. 3 825 16. 5 2. 24 25-30 130-135 3 Do. 9. 25 20. 75 412. 5 8. 25 6. 2 25-30 130-135 6 D0.

1 Oxyallzylationsusceptible compound. 2 In some instances Weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE XXIV Composition before-Amount of 080, catalyst and solvent constant before and after oxyalkyl- Composition at end Operating conditions a lOIl Ex. Weight ratio End product No. Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, as lyst, solvent, used, as EtO to PrO to BuO to pres, temp., of re- No. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxyalkylp.s.i. 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept suscept. cmpd. cmpdfi cmpd.

P1'O 135 720 24. 0# 8. 0 8.0 -15 125-130 4 Light amber heavy grease. 24. 0# 135 720 36.0 8. O 12.0 10-15 125-130 1% Vis. liquid. 36.0 135 720 45. 0 8. 0 15. 0 10-15 125-130 3 D0. 45. 0 135 720 51.0 8. 0 17.0 10-15 125-130 2 Do. 51.0 135 720 60.0 8.0 20.0 10-15 125-130 2% Do. OBuO 495 5, 400 4, 950BuO 16.0 .0 10-15 125-130 1% Dark anber vis.

iqui 4, 950 495 5, 400 16.0 2.0 10-15 125-130 1% Do. 9, 900 405 5, 400 16.0 2. 2 10-15 125-130 1% D0. 10, 890 495 5, 400 16.0 3. 0 10-15 125-130 3.0 Do. 14. 85 kg 495 5, 400 16. 0 6. 0 10-15 125-130 6. 0 Do. 11 z. OPrO 250 5. 5.0 8. 8 10-15 125-130 3. 0 Do. 122- 25.0 250 5. 25 10.0 8.8 10-15 125-130 3.0 Do. 132- 50.0 250 5.25 12.0 8. 8 10-15 125-130 1% Do. 142- 60. 0 250 5. 25 14. 0 8. 8 10-15 125-130 1% D0. 152- 70.0 250 5. 25 18. 0 8. 8 10-15 125-130 2 D0.

1 0xyalkylation-susccptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious. 3 Weight ratio based on original oxyalkylation susceptible compounds prior to any oxyalkylation.

TABLE XXV Composition beioreAmount of 050, catalyst and solvent constant before and after 0Xyalkyl- Composition at end Operating conditions ation End product EX Weight ratio Color and physical N state 080 1 Oxide Cata- Xylene Oxide Max. Max. Time Ex. 080 1 used, as lyst, solvent, used, as EtO to PrO to BuO to pres., temp, of re- No. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxyalkylp.s.i. C. action,

grams grams grams 2 ation ation ation hrs.

suscept. susccpt. suscept. cmpd. cmpd. cmpdfi 450 0Bu0 240 450BuO 8.0 20.0 1. 0 10-15 125-130 2 Lilght amber vis.

- i 450 450 45 240 900. 0 8.0 20. 0 2. 0 10-15 125-130 3 Do. 450 900 45 240 1, 350 8. 0 20. 0 3. 0 10-15 125-130 3% D0. 450 1,350 45 240 1,800 8.0 20.0 4.0 10-15 125-130 4 Do. 450 1, 800 45 240 2,250 8.0 20.0 5.0 10-15 125-130 5% Do. 495 013130 49. 5 540 495EtO 1.0 16.0 6.0 10-15 125-130 1 Dink admber vis.

iqui 405 495 49. 5 540 1, 485 3.0 16. 0 6.0 10-15 125-130 3 Do. 495 1, 485 49. 5 540 1, 930 4. 0 16. 0 6. 0 10-15 125-130 2 Do. 495 1,980 49. 5 540 2, 970 6. 0 16.0 6. 0 10-15 125-130 3% Very viscous. 495 2, 970 49. 5 540 3, 960 8.0 16. 0 6.0 10-15 125-130 3 Heavy to greasy. 450 OEtO 45. 0 472. 5 900 2. 0 18. 0 8.8 10-15 125-130 2 Vis. liquid. 450 900 45.0 472.5 3,600 8. 0 18.0 8.8 10-15 125-130 5% Very vis. liquid. 450 3, 600 45.0 472.5 4, 500 10.0 18.0 8. 8 10-15 125-130 2% Do. 450 4, 500 45.0 472.5 4, 950 11.0 18.0 8. 8 10-15 125-130 2 Do. 450 v 4, 950 45.0 472.5 5, 400 12.0 18. 0 8.8 10-15 125-130 2% Heavy to greasy.

Such change in unit is obvious.

prior to oxyalkylation.

employ what is a somewhat equivalent material, to wit, a dialkylaminocpoxypropane of the structure PART 5 As to the use of conventional demulsifying agents reference is made to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and patricularly to Part 3. Everything that appears therein applies with equal force and effect to the instance process, noting only that where reference is made to Example 13b in said text beginning I in column 15 and ending in column 18, reference should he to Example 5 herein described.

PART 6 wherein R and R are alkyl groups.

It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can be employed for The products, compounds, or the like, herein described can be employed for various purposes and particularly 7 the resolution of emulsions of the water-in-oil type and described in Part 5, preceding, and also for other purposes described hereinafter.

Not only may one use the oxyalkyl-ated derivatives herein described for a variety of purposes as enumerated previously and in greater detail hereafter, but one may also use the comparable derivatives obtained by reacting with polyepoxides and particularly diepoxides especially of the type known as the hydrophobe diepoxides and also the hydrophile diepoxides, Thus, such derivatives, or for that matter the esters, obtained by reaction with polycarboxy acids may be used in the resolution of petroleum emulsions.

All the various products, either those described in Part 4 or their derivatives as noted above, may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and Wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical pur-- poses.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from pctroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

Additional uses for products of the kind enumerated above, i.e., either the oxyalkylated derivatives as such or after further reaction, include their employment in a variety of materials, such as wetting agents or surface ten sion reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-in-Water emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

The products herein described can be reacted with polycarboxy acids such as phthalic acid, or anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical present in the final polyepoxide treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum emulsions of the water-in-oil type as herein described.

34- Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is,

1. The product obtained by a two-step manufacturing process consisting of first condensing (a) a fusible, non-oxygenated organic solvent-soluble, Water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic secondary amine free from any primary amino radical and having up to 32 carbon atoms in any group attached to any amino nitrogen radical and reactive towards glyoxal; and (c) a material selected from the group consisting of glyoxal, pyruvic aldehyde, alpha-hydroxyadipaldehyde, and alpha-gamma-dimethyl-alpha-methoxy- 30 methyl glutaraldehyde;

said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; the molar ratio of reactants (a), (b), and (0) being approximately 1, 2 and 1 respectively; the resinous condensation product resulting from the process being heatstable; followed by a second step of reacting said condensate with from one-half to fifty times by weight of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. The product of claim 1 wherein said material is glyoxal. 45 3. The product of claim pyruvic aldehyde.

4. The product of claim alpha-hydroxyadipa-ldehyde.

5. The product of claim 1 wherein said material is alpha-gamma-dimethyl-alpha-methoxymethyl glutaraldehyde.

1 wherein said material is 1 wherein said material is References Cited in the file of this patent UNITED STATES PATENTS 2,499,366 De Groote et al. Mar. 7, 1950 2,507,910 Keiser et al May 16, 1950 2,564,192 De Groote et a1. Aug 14, 1951 2,743,252 De Groote Apr. 24, 1956 2,792,366 De Groote May 14, 1957 

1. THE PRODUCT OBTAINED BY A TWO-STEP MANUFACTURING PROCESS CONSISTING OF FIRST CONDENSING (A) A FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND FROMALDEHYDE; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITLY GREATER THAN 2; SAID PHENOL BEING THE FORMULA 